Fast switch from extensional exhumation to thrusting of the Ronda Peridotites (South Spain)

The Alboran Domain, situated at the western end of the Mediterranean subduction system, is characterized by the Ronda Peridotites, one of the world's largest exposures of sub‐continental mantle. Using U–Pb (LA‐ICP‐MS) and Ar–Ar dating, we precisely dated two tectonic events associated with the Tertiary exhumation of the Ronda Peridotites. First, shearing along the Crust–Mantle Extensional Shear Zone caused, at ca. 22.5 Ma, mantle exhumation, local partial melting in the deep crust and coeval cooling in the upper crust. Second, the Ronda Peridotites Thrust triggered the final emplacement of the peridotites onto the continental crust at c. 21 Ma, as testified by granitic intrusions in the thrust hangingwall. The tectonic evolution of the western Alboran Domain is therefore characterized by a fast switch from continental lithospheric extension in a backarc setting, with sub‐continental mantle exhumation, to a rift inversion by thrusting driven by shortening of the upper plate.     

Systematics of metal-silicate partitioning for many siderophile elements applied to Earth’s core formation

Superliquidus metal-silicate partitioning was investigated for a number of moderately siderophile (Mo, As, Ge, W, P, Ni, Co), slightly siderophile (Zn, Ga, Mn, V, Cr) and refractory lithophile (Nb, Ta) elements. To provide independent constrains on the effects of temperature, oxygen fugacity and silicate melt composition, isobaric (3 GPa) experiments were conducted in piston cylinder apparatus at temperature between 1600 and 2600 °C, relative oxygen fugacities of IW−1.5 to IW−3.5, and for silicate melt compositions ranging from basalt to peridotite. The effect of pressure was investigated through a combination of piston cylinder and multi-anvil isothermal experiments between 0.5 and 18 GPa at 1900 °C. Oxidation states of siderophile elements in the silicate melt as well as effect of carbon saturation on partitioning are also derived from these results. For some elements (e.g. Ga, Ge, W, V, Zn) the observed temperature dependence does not define trends parallel to those modeled using metal-metal oxide free energy data. We correct partitioning data for solute interactions in the metallic liquid and provide a parameterization utilized in extrapolating these results to the P-T-X conditions proposed by various core formation models. A single-stage core formation model reproduces the mantle abundances of several siderophile elements (Ni, Co, Cr, Mn, Mo, W, Zn) for core-mantle equilibration at pressures from 32 to 42 GPa along the solidus of a deep peridotitic magma ocean (∼3000 K for this pressure range) and oxygen fugacities relevant to the FeO content of the present-day mantle. However, these P-T-fO₂ conditions cannot produce the observed concentrations of Ga, Ge, V, Nb, As and P. For more reducing conditions, the P-T solution domain for single stage core formation occurs at subsolidus conditions and still cannot account for the abundances of Ge, Nb and P. Continuous core formation at the base of a magma ocean at P-T conditions constrained by the peridotite liquidus and fixed fO₂ yields concentrations matching observed values for Ni, Co, Cr, Zn, Mn and W but underestimates the core/mantle partitioning observed for other elements, notably V, which can be reconciled if accretion began under reducing conditions with progressive oxidation to fO₂ conditions consistent with the current concentration of FeO in the mantle as proposed by Wade and Wood (2005). However, neither oxygen fugacity path is capable of accounting for the depletions of Ga and Ge in the Earth’s mantle. To better understand core formation, we need further tests integrating the currently poorly-known effects of light elements and more complex conditions of accretion and differentiation such as giant impacts and incomplete equilibration.     

Hypersaline fluids generated by high-grade metamorphism of evaporites: fluid inclusion study of uranium occurrences in the Western Zambian Copperbelt

In the Pan-African Lufilian belt (Western Zambian Copperbelt), uranium mineralizations, preferentially scattered in kyanite ± talc micaschists (metamorphosed evaporitic sediments) or concentrated along transposed quartz veins provide an opportunity to (1) understand the time/space relationship between the ore minerals and the deformation of the host rocks, (2) identify the different fluid events associated with specific stages of quartz deformation and (3) characterize the ore fluid geochemistry in terms of fluid origin and fluid/rock interactions. In the U occurrences studied in Lolwa and Mitukuluku (Domes region, Western Zambian Copperbelt), two mineralizing stages are described. The first generation of ore fluids (53–59 wt% CaCl₂, 13–15 wt% NaCl; N₂–H₂ in the gas phase of fluid inclusions) circulated during the high-temperature quartz recrystallization, at 500–700 °C. This temperature is in agreement with the P–T conditions recorded during the crustal thickening related to continental collision at ca. 530 Ma. LA-ICPMS analyses show the presence of uranium within this fluid, with a concentration mode around 20 ppm. The second generation of ore fluid (21–32 wt% NaCl, 19–21 wt% CaCl₂; CO₂–CO in the gas phase of fluid inclusions) percolated at lower temperature conditions, at the brittle–ductile transition, between 200 and 300 °C. This temperature could be related to the exhumation of the high-grade metamorphic rocks at ca. 500 Ma. The formation of H₂ and CO is interpreted as the result of radiolysis in the presence of dissolved uranium in the aqueous phase of these fluid inclusions. Finally, a late fluid (14–16 wt% NaCl_equiv) circulated in the brittle domain but seems unrelated to U (re-)mobilization event.     

Combining sensitivities and prior information for covariance localization in the ensemble Kalman filter for petroleum reservoir applications

Sampling errors can severely degrade the reliability of estimates of conditional means and uncertainty quantification obtained by the application of the ensemble Kalman filter (EnKF) for data assimilation. A standard recommendation for reducing the spurious correlations and loss of variance due to sampling errors is to use covariance localization. In distance-based localization, the prior (forecast) covariance matrix at each data assimilation step is replaced with the Schur product of a correlation matrix with compact support and the forecast covariance matrix. The most important decision to be made in this localization procedure is the choice of the critical length(s) used to generate this correlation matrix. Here, we give a simple argument that the appropriate choice of critical length(s) should be based both on the underlying principal correlation length(s) of the geological model and the range of the sensitivity matrices. Based on this result, we implement a procedure for covariance localization and demonstrate with a set of distinctive reservoir history-matching examples that this procedure yields improved results over the standard EnKF implementation and over covariance localization with other choices of critical length.     

Use of microfluidic experiments to optimize MICP treatment protocols for effective strength enhancement of MICP-treated sandy soils

Microbially induced calcium carbonate (CaCO₃) precipitation (MICP) has been extensively studied for soil improvement in geotechnical engineering. The quantity and size of calcium carbonate crystals affect the strength of MICP-treated soil. In this study, microfluidic chip experiments and soil column experiments were conducted to optimize MICP treatment protocols for effective strength enhancement of MICP-treated sandy soils. The microscale experiments reveal that, due to Ostwald ripening, longer injection intervals allow crystals to dissolve and reprecipitate into larger crystals regardless of the concentration of cementation solution. Even though a cementation solution input rate of 0.042 mol/l/h is sufficient to maintain a high chemical transformation efficiency, a further reduction in the input rate by about four times resulted in an increase in the size of crystals produced by the end of treatment from about 40 to 60 μm. These findings were applied in soil column experiments. Results showed that significantly larger crystals and higher soil strength were achieved when the normalized rate of cementation solution injection was reduced from 0.042 to 0.021 mol/l/h. Crystal size and soil strength increased slightly more when the normalized input rate was further reduced from 0.021 to 0.010 mol/l/h. This study demonstrates how data from microscale microfluidic experiments that examine the effects of injection intervals and concentration of cementation solution on the properties of calcium carbonate crystals can be used to optimize MICP treatment in macroscale sand soil column experiments for effective strength enhancement.

     

Block Simulation of Multiple Correlated Variables

Numerical representations of multivariate natural phenomena, including characteristics of mineral deposits, petroleum reservoirs and geo-environmental attributes, need to consider and reproduce the spatial relationships between correlated attributes of interest. There are, however, only a few methods that can practically jointly simulate large size multivariate fields. This paper presents a method for the conditional simulation of a non-Gaussian vector random field directly on block support. The method is derived from the group sequential simulation paradigm and the direct block simulation algorithm which leads to the efficient joint simulation of large multivariate datasets jointly and directly on the block support. This method is a multistage process. First, a vector random function is orthogonalized with minimum/maximum autocorrelation factors (MAF). Blocks are then simulated by performing LU simulation on their discretized points, which are later back-rotated and averaged to yield the block value. The internal points are then discarded and only the block value is stored in memory to be used for further conditioning through a joint LU, resulting in the reduction of memory requirements. The method is termed direct block simulation with MAF or DBMAFSIM. A proof of the concept using an exhaustive data set demonstrates the intricacies and the performance of the proposed approach.     

Modification of fluid inclusions in quartz by deviatoric stress. II: experimentally induced changes in inclusion volume and composition

Fluid inclusions in quartz are known to modify their densities during shear deformation. Modifications of chemical composition are also suspected. However, such changes have not been experimentally demonstrated, their mechanisms remain unexplained, and no criteria are available to assess whether deformed inclusions preserve information on paleofluid properties. To address these issues, quartz crystals containing natural CO₂–H₂O–NaCl fluid inclusions have been experimentally subjected to compressive deviatoric stresses of 90–250 MPa at 700°C and ~600 MPa confining pressure. The resulting microcracking of the inclusions leads to expansion by up to 20%, producing low fluid densities that bear no relation to physical conditions outside the sample. Nevertheless, the chemical composition of the precursor inclusions is preserved. With time the microcracks heal and form swarms of tiny satellite inclusions with a wide range of densities, the highest reflecting the value of the maximum principle stress, σ ₁. These new inclusions lose H₂O via diffusion, thereby passively increasing their salt and gas contents, and triggering plastic deformation of the surrounding quartz via H₂O-weakening. Using microstructural criteria to identify the characteristic types of modified inclusions, both the pre-deformation fluid composition and syn-deformation maximum stress on the host mineral can be derived from microthermometric analysis and thermodynamic modelling.     

Simulation of Geological Contacts from Interpreted Geological Model Using Multiple-Point Statistics

Applications of multiple-point statistics (mps) algorithms to large non-repetitive geological objects such as those found in mining deposits are difficult because most mps algorithms rely on pattern repetition for simulation. In many cases, an interpreted geological model built from a computer-aided design system is readily available but suffers as a training image due to the lack of patterns repetitiveness. Porphyry copper deposits and iron ore formations are good examples of such mining deposits with non-repetitive patterns. This paper presents an algorithm called contactsim that focuses on reproducing the patterns of the contacts between geological types. The algorithm learns the shapes of the lithotype contacts as interpreted by the geologist, and simulates their patterns at a later stage. Defining a zone of uncertainty around the lithological contact is a critical step in contactsim, because it defines both the zones where the simulation is performed and where the algorithm should focus to learn the transitional patterns between lithotypes. A larger zone of uncertainty results in greater variation between realizations. The definition of the uncertainty zone must take into consideration the geological understanding of the deposit, and the reliability of the contact zones. The contactsim algorithm is demonstrated on an iron ore formation.     

Trace element partitioning and substitution mechanisms in calcium perovskites

We have determined the partition coefficients of a large number of trace elements between CaTiO₃ perovskite and anhydrous silicate melts at atmospheric pressure and 3 GPa. Determination of the concentration limits of Henrys law behaviour in the CaO-Al₂O₃–SiO₂–TiO₂ system reveals that the incorporation of rare earth elements (REE) and tetravalent large ion lithophile elements (LILE⁴⁺ such as U and Th) at the Ca-site of CaTiO₃ perovskite occurs with charge compensation through Ca-vacancy formation rather than by coupled substitution of Al for Ti. When melt composition is varied, we find that partition coefficients for REE and Th are strong functions of the CaO content of the melt. The observed trends are in excellent agreement with those predicted from the Ca-vacancy model. Given that they adopt the same crystal structure and have similar trace element partitioning behaviour, CaTiO₃ perovskite and the deep mantle phase CaSiO₃ perovskite can be considered analogous to one another. When the analogy is pursued in detail, we find that partitioning into both phases follows the composition-dependence predicted by the Ca-vacancy model. Thus, substitution of REE, U⁴⁺ and Th into CaSiO₃ in the lower mantle also occurs with Ca-vacancy formation to balance charge. Furthermore when 2+, 3+ and 4+ partition coefficients for both phases are plotted as functions of CaO melt content, the trends for CaSiO₃ and CaTiO₃ appear to be continuous. This surprising result means that partitioning into Ca-perovskite is independent of pressure and temperature and also of whether or not the host is CaSiO₃ or CaTiO₃. One implication is that CaSiO₃ crystallising from a peridotitic magma ocean may have partition coefficients for Th and U up to about 400. Crystallisation and sequestration of as little as 0.25 volume% of this phase in the lower mantle early in earth history would make a significant contribution to current mantle heat production.Electronic Supplementary Material Supplementary material is available for this article at     

Silicate perovskite-melt partitioning of trace elements and geochemical signature of a deep perovskitic reservoir

We have determined the partitioning of a wide range of trace elements between silicate melts and CaSiO₃ and MgSiO₃ perovskites using both laser ablation-ICPMS and ion microprobe techniques. Our results show that, with the exception of Sc, Zr, and Hf, all trace elements we considered are incompatible in MgSiO₃ perovskite, from highly incompatible for U, Th, Ba, La, Sr and monovalent elements to slightly incompatible for heavy rare earth elements. MgSiO₃ perovskite-melt partition coefficients increase slightly with Al content in the perovskite. These observations contrast strongly with partitioning between CaSiO₃ perovskite and silicate melts. In the latter case, all rare earth elements are clearly compatible as are U and Th. Our data also suggest that, contrary to pressure and temperature, melt composition can significantly affect CaSiO₃ perovskite-melt partitioning; partition coefficients for rare earth elements and U and Th increase with decreasing CaO melt content. The presence of ∼0.4 wt% water in melt makes little difference, however. Partitioning of trace elements into the large site of both MgSiO₃ and CaSiO₃ perovskites follows the near-parabolic dependence on ionic radius predicted from the lattice strain model. The peaks of the parabolae are much higher for the CaSiO₃ phase, perhaps suggesting that the mechanisms of charge compensation for heterovalent substitution are different in the two cases. Our partitioning data have been used to assess the potential effect of perovskite fractionation into the lower mantle during early Earth history. Crystallisation of less than 8% of a mixture of CaSiO₃ and MgSiO₃ perovskites could have led to a ‘layer’ enriched in U and Th without disturbing the chondritic pattern of refractory lithophile elements in the primitive upper mantle. The resultant reservoir could have high Sm/Nd, U/Pb, Sr/Rb, Lu/Hf ratios similar to the HIMU component of ocean island basalts, but would not balance the observed depletion of the primitive upper mantle in Si and Nb.